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Patented Feb. 19, 1952 OFFICE POLYMER POLYSULFIDES CONTAINING ETHERGROUPS Frank K. Signaigo, Kenmore, N Y.

No Drawing. Application December 11, 1945, Serial No. 634,394

3 Claims. 1

My invention relates to a new class of products and methods whereby theymay be produced. More particularly, it relates to polyalkylenepolysulfides having lateral ether groups and methods whereby they may beprepared.

In my copending application Serial Number 470,909 of December 31, 1942,now abandoned, polymeric ethylene polysulfides and a method whereby theymay be prepared is disclosed. These compounds are useful for thepreparation of coatings, impregnations, cementing materials, and thelike. They are also valuable as oil resistant rubber-like materialssuitable for the manufacture of oil resistant hose. I have discoveredthat compounds having particular usefulness for the above mentionedpurposes and which are suitable for convenient preparation are obtainedwhen the polymeric ethylene polysulfides contain lateralether groups.

The polyalkylene polysulfides havin lateral ether groups as contemplatedin this invention have recurring structural units of the formula:

BrClEh-CHBr-CEQOCHa No.28

The preparation of my new class of products may be illustrated by thefollowing examples:

Example I.-A mixture of 252 parts (1 mol+%) of sodium sulfide(Na2S.9HzO), 68 parts (2 mols+5%) of sulphur, and 90 parts of water isstirred at 50 C. until all the sulphur is dissolved. To form magnesiumhydroxide, which acts as a dispersing agent in the subsequent polymerformation, 12 parts of sodium hydroxide are added, followed by thegradual addition with stirring of a solution of 30.6 parts of magnesiumchloride (MgClaGHzO) in 40 parts of water. the solution of sodiumpolysulfide maintained at about 50 C. is then added with stirring, overa period of 3 to 4 hours, 246 parts (1 mol) of 2,3-dibromopropyl ethylether (prepared by brominatin allyl ethyl ether in chloroform).

polymeric sulfide which separates is digested by stirring the reactionmixture at -75 C. for 7 to 8 hours. After cooling, the contents of thereaction vessel are poured into a large volume of water, and the solidis washed with water by de'cantation until the supernatant layer becomespale yellow, then air-dried.

Example 2.A mixture of 252 parts of sodium sulfide (NazSQHzO), 63 partsof sulfur, and parts of water is stirred at 50 C. until all the sulfuris dissolved. 16 parts of sodium hydroxide are added, followed by thegradual addition with stirring of all parts of magnesium chloride('MgCIaGI-IzO). To the solution of sodium polysulfide maintained atabout50 C. are then added with stirring, over a period of about 5 hours, 232parts of 2,3-dibromopropyl methyl ether (prepared by brominatingallylmethyl ether in chloroform).

The resulting polymeric sulfide which separates is digested by stirringthe reaction mixture at 70-75. C. for about 9 hours. After cooling, thepolymeric sulfide is filtered from the reaction mixture, washed oncewith a mixture of equal parts of water and ethyl alcohol, and dried atreduced pressure in a desiccator at room temperature, 193 parts ofpolymeric product being obtained.

Example 3.A solution of sodium polysulfide containing magnesiumhydroxide is prepared in the manner described in the preceding examplefrom 134 parts of sodium sulfide (NazSBHzO). 35 parts of sulfur, 50parts of water, 8 parts of sodium hydroxide, and 21 parts of magnesiumchloride hexahydrate. To this solution, maintained at about 50 C., areadded with stirring over a period of 2 hours, 132 parts of2,3-dibromopropylisopropyl ether (prepared by brominating allylisopropyl ether in chloroform). The polymeric sulfide which separates isdigested by stirring the reaction mixture for about 7 hours at 70-75" C.After cooling, the contents of the reaction vessel are poured intoWater, the solid washed with water and air dried.

Example 4.A mixture of 264 parts of sodium sulfide (Na -8.91120) and 71parts of sulfur is melted together by stirring at 50 C. To this solutionof sodium polysulfide, maintained at about 50 0., is added'dropwise withstirring, over a period of 5 hours, a solution of 274 parts of2,3-dibromopropyl n-butyl ether (prepared by brominating allyl n-butylether in chloroform) in 198 parts of methanol. The reaction mixture isthen stirred at 70-75 C. for an additional 18 hours to complete theformation of the polymer.

After standing at room temperature for about 16 hours, the polymericsulfide separates from the reaction mixture as a clear taffy-likematerial. It is washed by trituration with water and then with methanol,and is finally dried in a desiccator at reduced pressure.

The above described processes are only by way of illustration. Thepolymeric alkoxyethylene polysulfides derived from the methyL isopropyI,and n-butyl ethers of 2,3-dibromopropanol can be prepared by the processof the above examples. Polysulfides containing aromatic. alkyl-aromatic,cycloaliphatic or heterocyclic ether groups may also be prepared bygenerally similar processes from dihalogenoalkyl ethers having suchgroups attached to the ether oxygen atom.

My new polymeric alkylene polysulfides having lateral ether groups areviscous resins, insoluble in water but soluble in some organic solvents,as for example dioxane. They may be used as intermediates in thepreparation of vicinal dimercapto ethers by catalytic hydrogenation inthe presence of sulf-active catalyst, such as cobalt sulfide. Thepreparation of such monomeric ethers is disclosed by A. A. Pavlic and W.J. Peppel in application Ser. No. 568,064, filed December 13, 1944, nowPatent No. 2,397,689 issued April 2, 1946.

My invention is capable of wide variations from the form described, itsscope being defined in the appended claims.

What is claimed is:

1. The process of preparing a polymeric (methoxymethyl) ethylenepolysulfide characterized by the steps of mixing sodium sulfide, sulfur,and water in approximately the following proportions:

Parts Sodium sulfide (NazS.9HzO) 252 Sulfur 68 Water 90 adding 16 partsof sodium hydroxide, gradually adding with stirring 41 parts ofmagnesium chloride, then adding over a period of about 5 hoursapproximately 232 parts of 2,3-dibromopropylmethyl ether, and digestingthe resulting mixture by stirring for about 9 hours at 70-75 C.

2. The process of preparing a polymeric (methoxymethyD-ethylenepolysulphide consisting essentially of the reaction BrCH -CHBrCH:0CH$Na-ZS" cm-cl ver). ZNaBr where n is a small integer greater than 1 anda:

is an integer greater than 1.

3. As a new product, a polymeric (methoxymethyl) -ethylene polysulfidehaving recurrent structural units of the formula:

(CH2CHS,,),

omocm where n. is a small integer greater than 1 and :c is an integergreater than 1.

FRANK K. SIGNAIGO.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date I 2,195,380 Patrick Mar. 26, 1940FOREIGN PATENTS Nt f'1h6 Country Date 385,980 Great Britain Jan. 2, 1933446,173 Great Britain Apr. 20, 1936

3. AS A NEW PRODUCT, A POLYMERIC (METHOXYMETHYL) -ETHYLENE POLYSULFIDEHAVING RECURRENT STRUCTURAL UNITS OF THE FORMULA: